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Reiuued Jan. 25, 1938 I UNITED STATES 20.631; wnrrmc AGENTS BenJamin R.Harris, Chicago, 111., allignor to Oolgat'e-Balmolive-Peet Company,Jersey City, N. 8., a corporation of Delaware No Drawing. Original No.2,023,387, dated December 3, 1935, Serial No. 640,501, October 31. 1932.Application for reissue July 27, 193 7,

Serial No. 155,989

2-: cla ms.

, My invention relates to anew class of chemical substances, and more inparticular to anew class of chemical substances particularly'adapted foruse for detergent, penetrating, emulsifying, lathering flotation,anti-spattering or frothing purposes or reducing the surface tension ofwater.

In certain classes of industries, there is a need for a certain class ofchemical substances usuallyused in relatively small quantities butcapable of use in larger quantities to secure an effect principally theresult of a wetting action such as at a water-oil interface. In thetextile and leather treating industries, for example, there are manysituations where a wetting or detergent action is imperative and manydifferent chemical substances have been produced calculated to reducesurface tension and promote wetting in these industries. The use ofprior art substances has not been attended with unqualified success inall instances. In certain other types of industries, such as themargarine industries, for example, problems in preventing the spatteringof margarine in frying have arisen.

In one of my copending applications, I have described a new class ofsubstances possessing certain properties which lend themselves to beused in connection with oleomargarine to prevent the spattering of theoleomargarine during frying. As pointed out in this 'copendingapplication, Serial No. 566,156 filed September 30, 1931, as acontinuation in part of my prior application, Serial No. 475,622, filedAugust 15, 1930, the problem of preventing the spattering of margarineis considered by some investigators entirely a. matter of wetting. Inother words, this result is alleged to be accomplished by promotinggreater attraction between oleaginous and aqueous portions of theemulsion at the interface thereof. Although theproblem is probably notone of wetting action entirely, it appears that certain compounds, whichI describe in my .copending application, having the properties ofconcentrating at the water oil interface, will have an effect upon thespattering behavior of margarine. In view of the fact that many of thesubstances, which I have discovered and described in my copendingapplication, have a certain effect upon surface phenomena and are of acolloidal or semicolloidal nature, I have also found them useful in manyother industries functioning as softening,

wetting, emulsifying, detergent, lubricating, frothing, and penetratingagents in the arts where such agents are employed.

The principal object ofmy present invention is the provision of a newclass of chemical substances capable of satisfactory use in connectionwith the problems hereinabove discussed.

Another object is the. provision of a new class of chemical substanceswhich are in general of relatively, simple structure and can be cheaplymadein commercial quantities. w

Another object is the provision of a class of chemical substances of thecharacter set forth which in many instances will be innocuous andnon-toxic, even though employed in such foods as margarine.

Another object is the provision of a new class of chemical substanceshaving improved wetting characteristics.

Another object is the provision of a new class of substances with greatutility in the treating of textile materials.

Other objects and features of the invention will be apparent from aconsideration of the following detailed description.

Broadly speaking, t e classes of substances with which I am concernedare designated as hydrophillic lipins. One of the outstandingcharacteristics of the substances is the presence of lipophile andhydrophile groups in the molecule. A portion of the molecule has groupswhich are easily wetted by oils. This lipophile group in the substanceswhich I have investigated is a radical of predominately hydrocarboncharacteristics, though it may also be an alcohol, ether or ester group,or some other group as will appear from the illustrations given below.The lipophile group has marked afilnity for oils and fats, is readilycapable of being wet by oleaginous media, and, in general, at thewater-oil interface, tends to cause the molecule, of which it isa part,so to orientate itself, apparently, that the lipophile group may standin relatively closer proximity to the oil medium or phase, as contrastedwith the aqueous medium. The hydrophillic portion of the molecule is agroup which is easily wetted by water, and among these groups are suchgroups as OH groups or OH groups and sulphate groups. I have pointed outthat if the hydrophillic lipin contains a hydrophile group which willsufficiently balance the lipophile group, then such substance when usedin small proportions will act as an anti-spatterer preventing thespattering during frying of margarine made from milk and oleaginousmaterial.

The lipophillic group is preferably of moderately high molecular weight,as will be seen from illustrations given below; however, the preferredmagnitude of the molecular weight of the lipophillic group varies withthe character of the hydrophlllic group or groups coactlng with it.Generally speaking, sufllcient lipophllllc mass and quality must bepresent in the molecule to properly offset and balance the hydrophillicgroup. An excess of lipophillic characteristics is undesirable, since,in such a case, the substance as a whole becomes predominantlylipophile, becomes rather freely iat soluble, no longer orientatesitself at the interface of water and oil in the margarine emulsion andhence (assuming the employment of the substance in a margarineemulsion). largely loses its anti-spatterlng power.

' The above is merely a hypothesis which appears to lit the discoveredfacts and helps to explain them.

Chemically, the substances of my present invention are in general esterderivatives of moderately high or high molecular weight fatty acids orether derivatives of moderately high or high molecular weight alcohols,with at least oneseml-esterifled sulphuric acidgroup. In certaincircumstances, there may be more than one semiesterifled sulphuric acidgroup or there may be sulphuric acid groups that 'are totally esterifledand other sulphuric acid groups that are semi esterifled, but in allcases there must be at least one semi-esterified sulphuric acid group.

Considering the compounds from another aspect, the molecule in eachinstance contains a relatively high molecular weight lipophile group orgroups and a hydrophile group or groups which, in the 'class oi!compounds to which my present invention relates, are principallysulphuric acid radicals. From still another angle, the compounds may beconsidered as combinations of a higher molecular weight lipophile groupand the sulphate group linked together by means of a third group whichis generally a poly-hydrorw organic compound with at least twoesterifiable hydroxy groups. A more complete understanding of what maycomprise the lipophile groups and the intermediate radical which linksthe hydrophile group to the lipophile group will be had as the detaileddescription progresses.

I, therefore, have a substance containing a sulphategroup and alipophillic group of a sufficient molecular weight to balance thesulphate group. This substance may be a good anti-spattering substancewhen used in connectionwith margarine it the balance is suflicient; orit may function well in other industries as a wetting, penetrating,emulsifying, frothing, or detergent agent.

The function of the sulphuric acid groups is to impart hydrophillicproperties, that is, water wetting or water attracting properties, tothe molecule as a whole. The groups with which the.

sulphuric acid group is linked are in general of a lipophile character.At times they may be strongly lipophlllic and at other times moderatelylipophillic. They may be of comparatively low molecular weight or ofmoderately high molecular weight or of distinctly high molecular weight,depending upon the purpose for which the substance may be used.Furthermore, the group or groups with which the sulphuric acid isesterlned may have hydrophillic radicals 0! their own. An example ofthis type oi substance is lauryl glyceryl sulphate (sodium salt):

ONs

function is dependent principally upon the sulphate group. Furthermore,these two groups are linked together by means of a poly-hydroxysubstance, namely, glycerol.

Some additional examples of members of the group of substances which Ihave discovered are as follows:

' u HiC--0-C-(11Hu 0 Mono-oleyl' diethylene g glycol sulphate (potasH1CO-CHr-CH:0 =0 slum salt) on n 0 Cetl glycerol sulphate sodium salt)11 (Brie Pelmitl glycerol sul- I0 pirate sodium salt) 1[ -C Hr-0 i=0 KNa Mono-oleyl glycol sulphate (sodium ONe Sulphonated monostearylglucose.

triethylenc 4 unions 0 t H:-(" O CHEM (I) Palrnityl glycerol sulphate ll(II-C Hr-0- L =0 0 H H 0 Mono oloyltriethyleneglycol sulphate ifHaC0-CHr-CHr-0'C H=CH,0- =0 0 H l H1C- OC''CnHz3 Lauryl trimethylenegly- (u) col sulphate HzC -C 11 -0 Myristyl propylene glycol sulphate 1?H30 O S 0 Mali yl butylene glycol ate Melissyl butylene glycol sulphate(ammonium H salt) |C-O-'S=O ONH While the above list of the illustrativeembodiments of my invention indicates single, pure substances only, itmust be understood that mixtures may very well be used, either mixturesof single substances prepared independently or mixtures produced assuch, that is to say, instead of esterifying diethylene glycol withlauric acid and then esterifying the resultant ester with sulphuricacid, I can employ a mixture of coconut fatty acids, such as is obtainedfrom coconut oil, andesterify this mixture of fatty acids withdiethylene glycol to form a mixture of the mono fatty acid esters ofdiethylene glycol. This mixture I then esterify with sulphuric acid togive me the finished product.

As sources of the lipophile groupI can employ, for example, suchmaterials as melissic acid, stearic acid, oleic acid, ricinoleic acid,lauric acid, palmitic acid, cetyl alcohol, lauryl alcohol, cholesterol,mixed coconut fatty acids, mixed tallow fatty acids and other materialswith marked aflinity for. oils and fats.

For the purpose of linking the lipophile groups with the sulphate groupsI can employ such molecules as glycerol, diglycerol, polyglycerols,glycols, polyglycois, hydroxycarboxylic acids, sugars, alcoholderivatives of sugars, acid derivatives of sugars, and other diandpoly-hydroxy organic substances.

For the purpose of introducing the sulphate groups I may employsulphuric acid, concentrated or fuming, chlorsulphonic acid, sulphurylchloride, sulphur tri-oxide, solutions of sulphur trioxide and otherso-called sulphonating agents. The treatment with these agents may takeplace in the presence or absence of solvents and con densing agents suchas pyridine and the like.

The method for introducing the sulphate group difiers in diilerent casesand is dependent upon the material which is to be esterifled with thesulphuric acid and the purpose for which the resultant product is to beemployed.

An example of one of my methods is as follows: Monostearine is treatedat room temperature with 2 parts by weight of concentrated sulphuricacid (sp. gr. 1.84) and allowed to react about 15 hours. The product isthen washed substantially free of excess sulphuric acid and thenneutralized to form the salt or the sulphonated monostearine. Careshould be taken by mixing or otherwise to get the sulphuric acid into anintimate homogenous admixture with the monostearine. For'washing, hotbrine at a temperature of about 75f to C. gives the greatestsatisfaction inasmuch asunder these conditions the fat materialseparates in a distinct supernatant layer and facilitates the separationof the wash water in each successive washing. The product thus obtainedcontains a considerable proportion of water and in addition to theprincipal product, namely, monostearine sulphate (sodium salt), containsbesides, some unreacted monostearine and free stearic acid. If desiredthe substance may be purified.

Monolaurin and other mono fatty acid esters of glycerol and otherhydroxy organic substances may likewise be treated by the procedure justdescribed.

Still another satisfactory method is the one I followed in preparinglauryl diethylene glycol sulphate (ammonium salt) which is as follows:10 parts by volume of, monolauryl diethylene glycol dissolved in 20parts by volume of chloroform are cooled in ice water. 1 /2 parts byvolume of chlorsulphonic acid dissolved in 10 parts by volume ofchloroform are now slowly added with vigorous stirring to theflrstchloroform solution, at such a rate as not to raise the temperatureof the reaction mixture appreciably. After all the chlorsulphonic acidsolution has been introduced, the reaction mixture is aspirated with adry inert gas, to carry out most of the hydrochloric acid formed duringthe reaction. Finally, ammonia gas is passed into the mixture toneutrality. The chloroform may then be distilled oif or evaporated. Theproduct thus obtained has a remarkable power for lowering the surfacetension of water, even at very low concentrations, and has many otheruseful properties of the character described in the early part of thespecification.

Those of my substances which are freely soluble in water may berecovered from their solutions in the customary manner by concentratingand crystallizing. As the mass of the lipophile radical increases,solubility in water tends to decrease and afllnity for water ismanifested by dispersibility in water. From these aqueous dispersions mysubstances may be readily recovered by "salting ou with suitable solubleelectrolytes. Common salt is very satisfactory for this purpose in mostcases. When salted out of an aqueous dispersion at temperatures rangingfrom 60 to C., the substances are obtained in the form of a paste with awater content ranging from approximately 25 to 75 percent. The morehydrophylilc the substance, the greater the water wherein R. is analkyl, acyl, or some other lipophile group, 0 is oxygen, X representsthe residue of a polyhydroxy substance which links together thelipophile group with the hydrophyllic sulphate group, 5 stands forsulphur, Y is a cation, and w and v are small whole numbers, at leastone. I have also found that the addition of certain materials to thesubstances with which my invention is concerned, as hereinabovedescribed. markedly enhances their capacity to lower the surface tensionof water, their serviceability as "wetting-out agents" in the textiletreating industry, and markedly improves many of their other valuablecolloidal properties. These addition agents are principally the more orless lipophile ethers and esters of the hydroxy organic substances whichI employ for'esterifying with sulphuric acid or its equivalent in orderto produce the sulphuric esters described hereinabove. Notably usefulfor this purpose are monooleyl diethylene glycol, mixed mono acid estersof diethylene glycol with mixed coconut fatty acids, mixed mono acidesters of glycerol with mixed coconut fatty acids, mono caprylin and thelike.

Thus the addition agents are hydrophyllic lipins characterized by beingaliphatic derivatives of water soluble polyhydroxy substances having atleast one free OH group. While these hydrophyllic lipins in themselvesmay not be sufficlently balanced to have a marked effect either toprevent spattering of oleomargarine or decrease interfacial tension inwater-oil emulsions as in the case of the hydrophyllic lipins containinga semiesterized sulphuric acid group, they will have the eifect of somodifying the surface phenomena of the latter in contact with an aqueousmedium so as to affect the interfacial surface, surface tension and thepenetrating and wetting properties.

I have made extensive experiments to determine the effect of theaddition agents in increasing the wetting properties of my new sulphatecompounds. It will be sufficient for an understanding of this phase ofthe invention to give a few illustrative examples. In the case ofmonoolein di-sulphate which in itself is a good wetting agent, I foundthat substituting for some of the mono-olein di-sulphate in the treatingbath I found that the surface tension was decreased to 34 dynes percentimeter. In the same way, I found that while sulphates of mixedcoconut fatty acid esters of diethylene glycol were good wetting agents,the wetting action was greatly increased by the addition of a proportionof monooleyi diethylene glycol. In the case of monolaurin sulphate usedas a wetting agent, I found that I also obtained improved results by theuse therewith of a proportion of mono-caprylin. The surface tension ofwater underthe conditions in which the above data was established was'14 dynes per centimeter. By selecting one of the sulphate compounds ofmy present invention and a suitable addition agent of the classhereinabove described, I have found that very much better wetting actionis obtained than by the use of any other known wetting agent with whichI am familiar.

It will be noted that while my sulphuric esters in themselves produce aconsiderable lowering of surface tension, this effect is enhanced by theaddition of the fatty acid esters, notwithstanding the fact that theconcentration of the sulphuric ester proper is diminished.

It is to be noted that while I have chosen the lowering of the surfacetension of water as a convenient means of illustrating the eflfect ofthese addition agents, this surface tension lowering is by no meanstheir sole effect as they radically influence other valuable colloidalcharacteristics of the medium into which they are introduced as well asinfluencing the surface tension.

The substances which I add to my sulphuric esters for the purpose ofenhancing their useful colloidal properties, may be represented by thestructural formula:

News

wherein R is an aliavi. acyl or some other lipophile group, 0 is oxygen.H is hydrogen, :0 is a small whole number, at least one, and xrepresents the carbon skeleton of an organic hydroxy substance with atleast one free hydroxy group.

In the preceding specification, I have employed the term "hydrophylliclipin" in several places in a broad sense. That there may be nomisunderstanding of the use of this term, the manner in which it isused, and the relationship of the improved compounds of my inventionthereto, I wish to point out again from the standpoint of itsterminology the manner in which time compounds of my present inventionare produced.

I select preferably in the first instance a compound (or in some cases amixture of compounds) which has both a lipophillic group and ahydrophillic group. The compounds which I employ initially, however. aredominantly lipophlllic, the hydrophile group, in most cases for examplea single OH group, being of insufilcient strength or character to affectthe more dominant lipophile group to any great extent. I then attach tothe lipophile group, preferably at a hydroxy or carboxyl group, ahydroxy or poly-hydroxy substance which in itself has some hydrophilliccharacteristics. A suitable example as, previously set out are glycerolsand glycols and polycompounds thereof. I then attach a sulphate group tothe hydroxy radical by sulphonation, as previously described.

Substantially any process employed in producing the improved compoundsof my invention yields a material having a proportion of water mixedtherewith. In most cases the material is suitable for use in thiscondition without being dehydrated. It can be dispersed readily inadditional amounts of water down to concentrations of, for example,one-tenth per cent. as in the'illustration given above.

I however, the material may require dehydration In certain cases.

stance, sulphonation as employed in this specification denotes theformation of an ester of sulphuric acid.

I have described my invention in detail in order that those skilledinthe art may practice the same, but it is obvious that I do not restrictmyself to the specific details described, the invention being limitedonly by the scope of the appended claims.

The term poly" is used in the specification and claims in the usualsense, to denote more than one.

The term residue" is employed in its ordinarily accepted sense toconnote that which remains after the reaction of certain groups. Thus,for example, where glycerine, a polyhydroxy substance, is reacted with afatty acid, such as lauric acid, to produce a mono-ester and is thentreated with sulphuric acid or the like to produce mono laurin monosulphate, the residue" of the polyhydroxy substance is CH:- (IJHOHThroughout the specification and claims, the term residue is to beregarded as possessing the above connotation.

' What I claim as new and desire to protect by Letters Patent of theUnited States is:

1. A stable'chemical substance represented by the general formulawherein R is an acyl radical with at least four carbon atoms, Xrepresents the residue of an aliphatic polyhydroxy substance of a classconsisting of glycerol, polyglycerols, glycols, polyglycols,hydroxycarboxylic acids, sugars, sugar alcohols, and acid derivatives ofsugars which links together the acyl radical with the sulphate group, Yis a cation, and w and v are small whole numbers, at least one.

2. A stable chemical substance represented by the general formulawherein R is an acyl radical of a fatty acid with at least four carbonatoms, X represents a residue of glycerol which links together thesulphate group with the acyl radical, Y is a cation, and w and v aresmall whole numbers, at least one.

3. A chemical substance represented by the general formula wherein R isan acyl radical with at least four carbon atoms, X represents a residueof a glycol .which links together the sulphate group with the acylradical, Y is a cation, and w and v are small whole numbers, at leastone.

4. A chemical substance represented by the general formula wherein R isan acyl radical of a fatty acid with at least four carbon atoms, Xrepresents a residue of diethylene glycol which links together thesulphate group with the acyl radical, Y is a cation and w and v aresmall whole numbers, at least one.

5. A chemical substance represented by th general formula.

wherein X represents a residue of an aliphatic wherein R is an acylradical with at least four carbon atoms, X represents the residue of analiphatic polyhydroxy substance of a class consisting of glycerol,polyglycerols, glycols, polyglycols, hydroxycarboxylic acids, sugars,sugar alcohols and acid derivatives of sugars which links together theacyl radical with the sulphate group, Y is a cation, and w and v aresmall whole numbers, at least one.

9. A treating bath comprisng an aqueous liquid having dispersed thereina chemical substance other than sulphonated distearin and represented bythe general formula Maputo] Y.

wherein R is an acyl radical with at least four carbon atoms, xrepresents a residue "of glycerol which links together the sulphategroup with the acyl radical, Y is a cation, and w and v are small wholenumbers, at least one.

10. A treating bath comprising an aqueous solution having dispersedtherein a relatively small amount of esters of sulphuric acid of theeneral formula wherein R is an acyl radical with at least four carbonatoms, X represents the residue 01' an aliphatic polyhydroxy substanceof a class consisting of glycerol, polyglycerols, glycols, polyglycols,hydroxycarboxylic acids, sugars, sugar alcohols and acid derivatives ofsugars which links together the acyl radical with the sulphate group, Yis a cation and w and v are small whole numbers, at least one, andincluding as an addition agent a so,osc

relatively small amount of a hydrophillic llpln of the general formulawherein R is an akyl or acyl radical, w is a small whole number, atleast one, and X represents a residue of an aliphatic polyhydroxysubstance with at least one free hydroxy group.

11. A hydrated mixture of an ester of sulphuric acid of the generaliormula wherein R. is an acylrad ical with at least four carbon atoms, xrepresents a residue of an allphatic polyhydroxy substance of a classconsisting of glycerol, polyg cerols, glycols, polyglycols.hydroxycarboxylic acids, sugars, sugar alcohols and acid derivatives ofsugars which links together the acyl radical with the sulphate group, Yis a cation, and w and v are small whole numbers, at least one, andincluding a hydrophillic lipin of the general formula fiable hydroxygroups, wherein the hydrogen of at least one hydroxy group is replacedby a sulphate radical, and wherein the hydrogen of at least one otherhydroxy group is replaced by an acyl radical with at least four carbonatoms, said ester having hydrophillic properties, and wherein the otherhydrogen of the sulphate radical is replaced by a cation. I

16. An ester of sulphuric acid and an aliphatic dihydroxy substancewherein the hydrogen of one hydroxy group is replaced by a sulphateradical, and wherein the hydrogen of the other hydroxy group is replacedby an acyl radical with at least four carbon atoms, said ester havinghydrophillic properties.

17. A neutralized sulphuric'acid ester of a polyhydric alcohol, whereinthe hydrogen of at least one hydroxy group of the alcohol is replaced byan acyl radical with at least four carbon atoms, said ester havinghydrophile properties.

18. As new chemical compounds, sulphonated mixed mono-coconut fatty acidesters of diethylene glycol and salts thereof.

19. A mixture containing sulphonated mixed mono coconut fatty acidesters of diethylene glycol and mono coconut fatty acid esters ofdiethylene glycol and alkaline salts thereof.

20. As new chemical compounds, sulphonated mono higher fatty acid estersof a glycol and salts thereof.

21. As new 'chemical compounds, sulphonated mono higher fatty acidesters of a polyglycol and salts thereof. l

22. A mixture containing sulphonated mono higher fatty acid esters of apolyglycol and mono higher fatty acid esters of a polyglycol and saltsthereof.

23. An ester of sulphuric acid and an aliphatic polyhydroxy substance,wherein the hydrogen of at least one hydroxy group is replaced by anacyl radical of a normally liquid fatty acid. and wherein the hydrogenof at least one other hydroxy group is replaced by a sulphate radical.

24. A chemical substance represented by the general formula wherein R isan acyl radical of a fatty acid from cocoanut oil, x represents aresidue of glycerol which links together the sulphate group and the acylradical, and Y is a cation.

2s. a chemical substance represented by the general formula fatty acidmonoglycerides, the fatty acids .of which contain at least four carbonatoms;

mama HARRIS.

